Effect of secondary additives in casting solution on the performance of porous cellulose acetate reverse osmosis membranes

The solution structure and evaporation rate constant can be varied by changing the temperature of the casting solution and the temperature of the casting atmosphere for a given film-casting solution composition. The effects of the two temperature changes can be simulated (without changing the two temperatures) by replacing a small part of the solvent (acetone) by a secondary additive in the casting solution. The effect of 20 different secondary additives in the batch 316-type casting solution has been studied and is discussed. Porous cellulose acetate reverse osmosis membranes, capable of giving a 20% to 25% increase in productivity at a 90% level of solute separation for a 3500 ppm NaCl–H₂O feed solution at 250 psig, have been produced using 5 wt-% ethyl ether as the secondary additive in the above casting solution. The use of secondary additives offers a new flexibility in the choice of film-casting conditions and in the general development of reverse osmosis membranes.     

Studies on the development of improved reverse osmosis membranes from cellulose acetate–acetone–formamide casting solutions

Improved membranes from cellulose acetate–acetone–formamide casting solutions have been prepared for low-pressure reverse osmosis applications. The film-casting details for one such type of membranes (Batch 400) are as follows. Casting solution composition: cellulose acetate (E-398-3), 17 wt-%, acetone, 56 wt-%, formamide, 27 wt-%; temperature of casting solution, 24°C; temperature of casting atmosphere, 24°C; casting atmosphere, ambient air in contact with 30 wt-% acetone in aqueous solution; solvent evaporation period, 30 sec; gelation medium, ice-cold water. Using aqueous feed solutions containing 3500 ppm of NaCl, the product rates obtained with the above membranes at 95, 90, and 60% levels of solute separation were 15.9, 22.1, and 58.7 gallons/(day ft²), respectively, at 250 psig under feed flow conditions corresponding to a mass transfer coefficient of 45 × 10^?4 cm/sec on the high-pressure side of the membrane. The effects of casting solution composition, presence of acetone in the casting atmosphere, evaporation period, evaporation rate constant, and the remoteness of casting solution composition from the corresponding phase boundary composition on membrane performance and shrinkage temperature profile were found to be similar to those reported earlier for membranes obtained from cellulose acetate–acetone–aqueous magnesium perchlorate casting solutions. The results illustrate the practical utility of the approach based on the solution structure–evaporation rate concept for creating more productive reverse osmosis membranes.     

Development and performance of some porous cellulose acetate membranes for reverse osmosis desalination

The effects of casting solution composition and evaporation period on the performance of resulting porous cellulose acetate membranes have been studied, and the results are discussed in terms of casting solution structure, solvent evaporation rate during film formation, and the film shrinkage temperature profile. The development of Batch 316-type porous cellulose acetate membranes is reported. At 90% level of solute separation and feed flow conditions corresponding to a mass transfer coefficient of 45 × 10^?4 cm/sec, the productivities of the above membranes are 21.5 gallons/day/ft² at 250 psig using 3500 ppm of NaCl in the feed, and 53.9 gallons/day/ft² at 600 psig using 5000 ppm of NaCl in the feed.     

Cellulose acetate ultrafiltration membranes

Twenty-three different casting solution compositions involving cellulose acetate E-938-3 (polymer, P), acetone (solvent, S), and aqueous magnesium perchlorate (Mg(ClO₄)₂:H₂O = 1:8.5) (nonsolvent, N) were studied for making ultrafiltration membranes. These compositions (expressed in weight units) involved N/P ratios of 0.817 to 1.3 and S/P ratios of 3.5 to 5.33. It was found that by adjusting the values of S/P and N/P ratios in the casting solution composition, temperature of the casting solution, temperature of the casting atmosphere, and solvent evaporation period during film formation, a wide variety of cellulose acetate membranes useful for both ultrafiltration and reverse osmosis applications could be obtained. The results of a continuous test run at 50 psig for a period of 250 hr with a typical set of membranes, and their separation characterstics for a group of solutes ranging in molecular weight from 58 to 160,000, are presented.     

Improvement of porous cellulose acetate reverse osmosis membranes by change of casting conditions

The effects of temperature of casting solution in the range ?10° to 15°C, that of casting atmosphere in the range 10° to 30°C, relative humidity of casting atmosphere in the range 35% to 75%, and solvent evaporation period in the range 0.5 to 3 min were studied on shrinkage temperatures, solute separations, and product rates of Loeb-Sourirajan-type cellulose acetate membranes in reverse osmosis experiments. The composition of casting solution used was as follows: cellulose acetate, 17; acetone, 69.2; magnesium perchlorate, 1.45; and water, 12.35 wt-%. Best performance was obtained with membranes cast under the following conditions: temperature of casting solution, 10°C; temperature of casting atmosphere, 30°C; relative humidity of casting atmosphere, 65%; and solvent evaporation period, 1 min. For a 90% level of solute separation, the productivities of the above type of membranes were 22.9, 61.4, and 64.5 gallons/day-ft² at 250, 600, and 1500 psig using 3500 ppm NaCl–H₂O, 5000 ppm NaCl–H₂O, and 28395 ppm NaCl–H₂O feed solutions, respectively. In all cases, the feed flow rates corresponded to a mass transfer coefficient of 45 × 10^?4 cm/sec on the high-pressure side of the membrane. The general specifications of the above type of membranes are given for the operating pressures of 250, 600, and 1500 psig. The effects of the above casting condition variables on the surface pore structure during film formation are discussed.     

Development and characterization of cellulose acetate benzoate flat osmotic membranes

Different parameters of casting solutions and casting conditions were studied for the development of cellulose acetate benzoate flat osmotic membranes. Casting solutions were prepared with different concentrations of the polymer, the additive, and the solvent; viscosity of the casting solution; and the thickness of the membrane developed. The membranes were given different evaporation periods and annealing temperatures under different RH. Different annealing baths were also used. Based on these, conditions were optimized for the development of cellulose acetate benzoate flat osmotic membranes. These membranes were characterized with respect to bound water content, specific water content, transport properties by direct osmosis, salt intake by direct immersion, water permeability coefficient of the dense membrane, diffusion coefficient, salt permeability, and salt distribution by electrical conductivity. Also, cellulose acetate benzoate membranes were compared with conventionally used cellulose acetate membranes. © 1994 John Wiley & Sons, Inc.     

An approach to the development of cellulose acetate ultrafiltration membranes

The film-casting solution consisted of a mixture of cellulose acetate, acetone, and aqueous magnesium perchlorate [Mg(ClO₄)₂:H₂O = 1:8.5], designated as polymer P, solvent S, and nonsolvent N, respectively. Using the composition P:S:N = 17: 69.2: 13.8 as reference, films were obtained from 19 different casting solutions in which the weight ratios S/P, N/S, and N/P were varied in different directions. The casting solution temperature was 0°C, and solvent evaporation period during film formation was minimum in most cases. The effects of variations of casting solution temperature and solvent evaporation period were also briefly studied. Reverse osmosis experiments with resulting membranes were carried out at 100 psig using 200 ppm NaCl–H₂O as the feed solution. Decrease in S/P, increase in N/S, and increase in N/P in the casting solution, decrease in temperature of the casting solution, and increase in solvent evaporation period tend to increase the size of pores on the surface of resulting membranes in the ascast condition. Increase in S/P in the casting solution, and increase in the temperature of the casting solution tend to increase the effective number of pores on the membrane surface. These results offer definitive physicochemical criteria in terms on solution structure–evaporation rate concept for developing useful cellulose acetate ultrafiltration membranes.     

Evaporation rate and equilibrium phase separation data in relation to casting conditions and performance of porous cellulose acetate reverse osmosis membranes

Quantitative data on solvent evaporation rates and equilibrium phase separation compositions corresponding to different film casting conditions are given, and the results are discussed with reference to reverse osmosis data on membrane performance. A typical evaporation rate curve plotted on a semilog scale consists of an initial linear part from whose slope evaporation rate constants b have been determined. For a given casting solution composition and temperature, an optimum value of b exists for best membrane performance, and identical values of b result in same membrane performance. Treating the casting solution as a polymer–solvent–nonsolvent ternary system, the data on equilibrium phase separation compositions have been plotted in a triangular diagram for solution temperatures of ?10°, 0°, and 24°C. The data indicate that even small changes in solution temperature can bring about significant changes in solution structure and hence membrane performance, and useful conclusions on solution structure can be drawn from such phase equilibrium diagrams. The data and correlations presented here offer a quantitative confirmation of the governing significance of the solution structure-evaporation rate concept relating to the mechanism of phase separation and pore formation in the surface region during the process of making reverse osmosis membranes.     

Effect of ethanol–water mixture as gelation medium during formation of cellulose acetate reverse osmosis membranes

By using ethanol–water mixtures in a wide range of alcohol concentrations and temperatures, cellulose acetate membranes with a wide range of surface porosities can be obtained. Two different casting solution compositions were used, involving cellulose acetate, acetone, and aqueous magnesium perchlorate (composition I) or formamide (composition II). All reverse osmosis experiments were carried out at 250 psig using a 3500 ppm NaCl–H₂O feed solution at laboratory temperature. The effective area of film surface was 12 cm² in all cases. With composition I, with pure water gelation medium at 0°C, the resulting membrane gave a solute separation of 5% and product rate of 220 g/hr, whereas with 95% alcohol as gelation medium, the resulting membrane gave a solute separation of ～1% and product rate of 1240 g/hr under otherwise identical experimental conditions. With composition II membranes, the maximum product rate of 360 g/hr with the corresponding minimum solute separation of ～1% was obtained with 71.2% alcohol–water gelation medium at 0°C. Increase in the temperature of the gelation medium in the range 12° ?25°C tends to increase the average size of pores on the membrane surface. These results offer a basis for the development of cellulose acetate ultrafiltration membranes.     

Improved cellulose acetate membranes for reverse osmosis

Performance of cellulose acetate membranes in reverse osmosis varies with the conditions under which they are cast. By varying casting solution composition and holding time in a systematic way, improvement in water flux at a given level of salt rejection has been obtained. Statistically designed experiments have been helpful in optimizing these two variables. A phase diagram of the cellulose acetateformamide-acetone casting system has been determined which gives the region of natural solubility of this three component system.     

On the structure of concentrated cellulose acetate solutions

The supermolecular structure of cellulose acetate membrane casting solutions was determined by measuring their rheological behavior. The method was applied to both clear and turbid casting solutions. The resulting data on activation energy of viscous flow are shown to depend on the cellulose acetate content of the casting solution and on the nature of solvent used. The separation properties of the prepared asymmetric membranes determined by reverse osmosis testing indicate a good correlation with the data obtained by the rheological measurements of the casting solutions. The latter can, therefore, be used as a practical tool for the investigation of early stages in the asymmetric membrane formation process.     

Studies on syntheses and permeabilities of special polymer membranes. V. Effect of casting solution composition on permeation characteristics of cellulose acetate membranes in separation of aqueous polymer solutions

The permeation characteristics of cellulose acetate membranes in separation of polymers from their aqueous solutions were investigated by changing the preparation conditions of the membranes, that are the solvent evaporation period and the casting solution composition consisting of a mixture of cellulose acetate (CA), acetone (A), and formamide (FA). The rates of pure water permeability were influenced remarkably by the solvent evaporation period and the casting solution composition. When the solvent evaporation period was short, the rates of pure water permeability increased with a decrease in A/CA, increase in FA/A, and increase in FA/CA in the casting solution. From the experimental results using poly(vinyl alcohol) as poly(ethylene glycol) as feed solute, it was seen that the changes of solvent evaporation period and casting solution composition related to the change of microporous structure of the resulting membranes. The effect of feed concentration and operating pressure on the permeation characteristics were also studied. There was found a concentration polarization of poly(vinyl alcohol) molecules on the surface of the membrane, and a compaction of the membrane occurred under pressure.     

Effects of Membrane-Making Conditions and Shrinkage Treatment on Morphology and Performance of Cellulose Acetate Butyrate Membranes

Abstract

The functions of additives in cellulose acetate butyrate (CAB) membrane casting solution, effect of thermal shrinkage treatment on porous CAB membranes, and the changes of CAB membrane surface morphology during the solvent evaporation step have been investigated. Additives (glycerol and lactic acid) in CAB membrane casting solution function only as pore number promoting agents when used at low concentration and function both as pore number and pore size promoting agents when used at higher concentrations. Triethyl phosphate in CAB membrane casting solution functions both as a pore number promoting agent and as a secondary solvent for CAB. Three distinct phases can be observed in the solvent evaporation step in making CAB membranes. With the increase in solvent evaporation time, the number of pores in the first pore size distribution increases in the initial small pore-forming phase and decreases in the large pore-forming phase, and the number of pores in the second pore size distribution always increases with solvent evaporation time. These changes in pore numbers, pore sizes, and pore number ratio in two pore size distributions as well as the membrane skin layer thickness together govern the ultimate membrane performance and result in a maximum solute separation which, in the case of CAB/ acetone membranes, falls at 60 seconds of solvent evaporation time. Significant improvement of the performance of a porous CAB membrane can be achieved by thermal shrinkage treatment. Equally high CAB membrane performance can also be achieved by using a lower concentration of additives in the membrane casting solution.     

Investigations on nylon 4 membranes: Synthesis and transport properties. II. Transport properties of nylon 4 polymer membranes

The reverse osmosis, ultrafiltration, and dialysis properties of nylon 4 membranes to separations of sodium chloride, urea, a series of ethylene glycols and other compounds in the aqueous phase were investigated. The nylon 4 membranes were prepared from a formic acid solution with and without organic or inorganic additives. The effects of polymer concentration, amount of additives, casting time, and temperature on the membrane performance in terms of salt separation and product rate were investigated. The tensile properties of the nylon 4 membranes in both the dry and wet states were determined. It was found that the highest salt separation of a 0.1% sodium chloride solution did not exceed 53.3%. However, these membranes showed some intersting dialysis properties which were comparable to those of commercial cellophane and cellulose acetate membranes.     

Microstructure and ordering in cellulose acetate and reverse osmosis membranes

The performance of cellulose acetate reverse osmosis membranes for desalination or purification is greatly affected by the microstructure of the membrane. It is, therefore, highly desirable to characterize the microstructure and its dependence on preparation conditions and past history. In this study, various types of cellulose acetate powders, flakes, and solvent cast films have been characterized by differential scanning calorimetry and thermo-optical analysis. It is shown that ordered microstructures exist in many of these samples and that this ordering can be intensified or diminished by suitable treatments. It is conjectured that a similar microordering occurs in the dense layer of asymmetric cast membranes as a result of solvent evaporation, gelation and annealing and that the extent of orientation and chain packing in the ordered regions greatly affects the performance of reverse osmosis membranes.     

Reverse osmosis separation of phenols in aqueous solutions using porous cellulose acetate membranes

Reverse osmosis separations of phenol (9.4 to 108 ppm), p-cresol (108 ppm), and p-chlorophenol (129 ppm) were studied using Loeb-Sourirajan-type porous cellulose acetate membranes, and single-solute aqueous feed solutions at 500 psig and the indicated solute concentrations. It was found that, by dissociating the solute by changing the pH of the feed solution, all the above phenols could be separated by reverse osmosis. Solute separation increased with increase in the degree of dissociation of the solute in the feed solution; and, by the appropriate choice of pore size on the membrane surface, separations of phenol approaching the degree of dissociation of phenol in the feed solution could be obtained under the operating conditions used. Similar experiments using aniline (93 ppm) as the solute showed that dissociation of solute molecules in the feed solution could be a technique generally applicable for the reverse osmosis separation of nonionic solutes in aqueous solution. The effects of operating pressure in the range 250 to 1500 psig and pore size on the membrane surface on the separation of un-ionized phenol and p-chlorophenol showed that, with respect to single-solute aqueous feed solutions of phenols, the component whose relative acidity was greater was preferentially sorbed at the cellulose acetate membrane—aqueous solution interface, and the solute concentration in the membrane-permeated product solution was a function of the extent and mobility of each of the sorbed species.     

Structure of porous cellulose acetate membranes and a method for improving their performance in reverse osmosis

Experimental data support the hypothesis that the surface layer of the asymmetric Loeb-Sourirajan type porous cellulose acetate membranes has a heterogeneous microporous structure. A general method is proposed for improving the performance of the above membranes in reverse osmosis, by which product rates are increased without decreasing solute separation. The method consists in pumping pure water past the back side of the membrane under just enough pressure for a sufficiently prolonged period of time; after such pretreatment, the membrane is used in the reverse osmosis experiments in the normal manner with the surface layer facing the feed solution. Back-pressure treatment at 400 psig for 85 hr on preshrunk and normally pressure-treated membranes increases the product rate by over 20% without decreasing solute separation in reverse osmosis experiments at 600 psig with the use of 0.5 wt-% NaCl–H₂O feed solutions; with a different sequence of back-pressure treatment, similar results have been obtained in reverse osmosis experiments at 1500 psig also. The compaction effect of a normal membrane and that of a back pressure treated membrane are the same during continuous reverse osmosis operation under 600 psig; the effects of back-pressure treatment on a normal membrane and a compacted membrane are also the same. The pure water permeability data obtained in cyclic experiments show that the smaller pores on the surface layer are opened more than the bigger ones during the back side operation. The probable structural changes taking place in the film during back-pressure treatment are discussed.     

Studies on syntheses and permeabilities of special polymer membranes. X. Effects of conditions of membrane preparation on permeation characteristics of cellulose acetate membranes in separation of aqueous polymer solutions

The effects of casting solvents, dissolution temperature of casting solution, and pH and temperature of gelation solution, etc. on the permeation characteristics of cellulose acetate membranes in the separation of polymers from their aqueous solutions were investigated, using aqueous solutions of poly(ethylene glycol) and poly(vinyl alcohol) as feed. The permeation characteristics were influenced significantly by the conditions of membrane preparation and of the permeation. It was found that a concentration polarization at the membrane surface occurred with poly(vinyl alcohol) molecules, but it was very small with poly(ethylene glycol). The above results were discussed in detail from points of view of structure of the resulting membranes and the interactions between the solvent, the solute in the feed and the cellulose acetate molecules.     

Spinning of cellulose acetate hollow fiber by dry-wet technique of 3C-shaped spinneret

Cellulose acetate hollow fibers were spun by a new method—a dry–wet spinning technique of a 3C-shaped spinneret. The spinning technique parameters effecting the form and the reverse osmosis performances of the hollow fiber were investigated in detail, such as polymer concentration, the kind of solvent and additive, spinneret temperature, extrasion rate, evaporation distance, and take-up rate. Heat treating for different times in several treating baths was tested. The results showed that cellulose acetate hollow fiber spun by this method is feasible and is a kind of “loose” reverse osmosis membrane and suitable to operate at ultralow pressure, 0.8 MPa, and exhibits a higher flux rate at a salt rejection of 60–85% for tap water. Cellulose acetate hollow fiber for ultralow pressure reverse osmosis should find wide application in industrial processes. © 1996 John Wiley & Sons, Inc.     

Determination of concentration changes on membrane surface as function of time during evaporation of reverse-osmosis film casting solutions

Data on the activity of acetone for the binary system acetone-formamide, and a specific ternary system cellulose acetate-acetone-formamide are given for the temperature range 0 to 30°C. A method of determining concentration changes occurring on the membrane surface during the evaporation stage in the process of making cellulose acetate reverse osmosis membranes is illustrated.